Method for the production of certain aromatic and hetero-aro- matic aldehydes



United States Patent Ofice Reissued Sept. 20, 1971 27,171 METHOD FOR THE PRODUCTION OF CER- TAIN AROMATIC AND HETERO-ARO- MATIC ALDEHYDES Robert K. Grasselli, Garfield Heights, Ohio, assignor to The Standard Oil Company, Cleveland, Ohio No Drawing. Original No. 3,452,032, dated June 24, 1969,

Ser. No. 623,563, Mar. 16, 1967, which is a continuation-in-part of Ser. No. 450,537, Apr. 23, 1965. Application for reissue Aug. 25, 1969, Ser. No. 860,126

Int. Cl. C07d 31/32; B013 11/32 U.S. C]. 260-297 9 Claims Matter enclosed in heavy brackets appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.

ABSTRACT OF THE DISCLOSURE The instant invention relates to a direct-catalytic process for making monoolefinically unsaturated aromatic aldehydes from allyl substituted aromatic compounds.

This application is a continuation-in-part application of copending application Ser. No. 450,537, filed Apr. 23, 1965, now Patent No. 3,325,504 granted June 13, 1967.

The present invention relates to a process for the manufacture of monoolefinically unsaturated aromatic nitriles and aldehydes from certain substituted allyl aromatic compounds. More particularly, it relates to a direct process for converting compounds having the structure wherein A is an aromatic radical such as phenyl, naphthyl, pyridyl, quinolyl, anthryl or phenanthryl and R is either hydrogen or a hydrocarbon group having from 1 to carbon atoms, to monoolefinically unsaturated aldehydes by catalytic reaction with molecular oxygen or to monoolefinically unsaturated nitriles by catalytic reaction with molecular oxygen and ammonia. For example, allyl benzene may be converted to cinnamaldehyde or to cinnamonitrile with high yields.

In the past, processes for the preparation of cinnamaldehyde or cinnamonitrile have generally involved several steps and usually produced relatively low yields of rather impure products. More recently a direct, onestep catalytic process has been discovered wherein [3- methyl styrene is converted to cinnamaldehyde or cinnamonitrile and this process is more fully described and claimed in the copending US. patent application of R. K. Grasselli and J. L. Callahan, Ser. No. 423,818 filed Jan. 6, 1965, now Patent No. 3,435,061 granted Mar. 25, 1969. The reaction in this recently discovered process is comparatively straightforward and the yields are fair. Surprisingly, the reaction of the instant process starting with the substituted allyl aromatic compound, though it apparently involves an electronic rearrangement, gives exceptionally good yields.

It is an object of this invention to produce directly from an allyl aromatic compound such as allyl benzene the aldehyde and nitrile compounds such as cinnamaldehyde and cinnamonitrile. This may be accomplished, for example, by reacting allyl benzene with a reactant such as (1) oxygen and (2) oxygen and ammonia, in the presence of any one of several oxidation catalysts, and preferably a catalyst comprising antimony oxide as an essential ingredient in combination with at least one other polyvalent metal oxide, hereinafter more fully disclosed.

Several catalysts have been found to be operative in the process of this invention. In general, the oxides of one or more polyvalent metal elements are useful as catalysts in the process of this invention. More particularly, the useful catalysts for this process are those composed of at least one oxide of an element appearing in Groups I-B, II-B, IV-A, V, VI-B, VIIB, and VIII of the Mendelyeev Periodic Table (see Handbook of Chemistry and Physics, 38th Edition, Chemical Rubber Publishing Co., Cleveland, Ohio, pp. 394-395). Operative catalysts include the combined oxides of antimony and at least one other polyvalent metal such as the combined oxides of antimony and uranium, the combined oxides of antimony and iron, the combined oxides of antimony and manganese, the combined oxides of antimony and thorium, the combined oxides of antimony and cerium and the combined oxides of antimony and tin and mixtures of one or more of the foregoing combinations of oxides.

Other catalysts useful in this invention are composed of at least one salt of molybdic, phosphomolybdic, tungstic, and phosphotungstic acids with an element appearing in Groups IB, lI-B, IV-A, V, VI-B, VII-B and VIII of the Mendelyeev Periodic Table. Operative catalysts include bismuth molybdate, bismuth phosphomolybdate, antimony-bismuth molybdate, antimonybismuth phosphomolybdate, bismuth phosphotungstate, bismuth silicomolybdate, bismuth silicophosphomolybdate, bismuth silicotungstate, bismuth silicophosphotungstate and mixtures of one or more of the foregoing combinations of salts.

Promoter metal oxides incorporated in the catalyst so as to comprise up to 15% by weight thereof, based on the weights of the elemental metals, may be used effectively, but amounts up to 5% by weight of one or more promoter oxides are preferred.

The catalysts useful in the present invention may be used alone or supported on or impregnated in a carrier material. Any suitable carrier material may be used, including silica, alumina, thoria, zirconia, titania, boron phosphate, silicon carbide, pumice, diatomaceous earth, clay and the like. In general, the support will be employed in amounts less than by weight of the final catalyst composition.

The catalysts useful in the present invention may be prepared in numerous ways known in the art. For instance, the catalysts may be manufactured by co-gelling the various ingredients and drying or by spray-drying, extruding or spherulizing in oil.

The catalyst may be calcined to produce desirable physial properties such as attrition resistance, surface area and particle size. It is preferred that the calcined catalyst be further heat-treated in the presence of oxygen at an elevated temperature above 500 F. but below a temperature deleterious to the catalyst. For the purpose of the present invention, a catalyst having a particle size between 1 and 500 microns and a surface area in the range from 1 to 25 square meters per gram is preferred.

In the process for the manufacture of monoolefinically unsaturated aromatic nitriles and aldehydes e mbbdied herein, the temperature may be any temperature in the range from 200 to 800 C., the preferred range being 350 to 500 C.

The pressure at which the instant reaction is conducted is an important variable; a preferred pressure for conducting the reaction is from about 1 to 3 atmospheres so that the yield of undesirable by-products is minimized.

The apparent contact time employed in the process of this invention should be kept within certain limits to ob tain good selectivity and yields. The apparent contact time may be defined as the time in seconds a unit volume of gas, measured at reactor conditions of temperature and pressure, is in contact with the apparent unit volume of catalyst. It may be calculated, for instance, from the apparent volume of the catalyst bed, the average temperature and pressure of the reactor and the mass flow rate of the reaction mixture. The optimum contact time will depend upon the particular alkyl substituted aromatic hydrocarbons being oxidized or ammoxidized. A contact time from 0.01 to 50 seconds may be used, though a contact time of 0.1 to seconds is preferred.

Molar ratios of air to the vinyl substituted aromatic hydrocarbon may vary from approximately 1:5 to 1:200. Ratios near the high limit make for poor selectivity, while ratios near the low limit decrease catalyst activity. Preferred molar ratios of air to hydrocarbon are in the range of 1:10 to 1:100.

No ammonia is present in the feed when the vinyl Substituted aromatic is to be oxidized to the corresponding aldehyde, but only when the ammoxidation reaction producing the nitrile is to be conducted. In this latter case, up to 20 moles of ammonia per mole of hydrocarbon are found to be effective. For economic reasons, approximately stoichiometric quantities of hydrocarbon feed and ammonia are preferred.

Any molecular oxygen containing gas can be used in this process. Oxygen itself may be used without any diluent, although it is usually desirable to use in addition to oxygen at least one diluent such as steam, carbon dioxide, nitrogen and the inert gases. Any molar ratio of diluent within the range of 1:1 to 1:100 may be used, but the range from 1:50 to 1:75 gives satisfactory control of the reaction in either a fixed bed or fluidized bed reactor.

The equipment required for the reaction may be the standard type used for carrying out vapor phase oxidation reactions, such equipment being well-known to those skilled in the art. For the experimental work in the present invention, a tubular fixed bed reactor, equipped with an injection system was immersed in a molten salt bath. The gaseous reactants and diluents were introduced from pressurized containers fitted with pressure regulators, and the amount introduced was measured by flow meters.

The reactants are introduced into the reactor either at reaction temperature by first passing them through a preheater zone or by introducing them directly into the reactor and allowing them to come to reaction temperature as they travel through the catalyst bed.

The reaction products can be recovered by any desirable method. One method is the use of solvent scrubbers. A preferred method is the use of one or more Dry Ice traps in series while serve to isolate the reaction products by condensing them. The products of reaction were analyzed using standard techniques including gas chromatography, infrared analysis and nuclear magnetic resonance.

5 While only the preferred form of the invention is described in detail, it will be apparent to those skilled in the art that various modifications may be made therein without departing from the scope of the invention or the scope of the appended claims.

In the examples the following definitions are employed:

Conversion-carbon basis Weight of carbon in the products of reaction Weight of carbon in the propylene feed EXAMPLES 1-12 Several runs made with dilferent catalysts using allyl benzene for feed are set forth in table below. For purposes of comparison, the same catalysts were used with ,B-methyl styrene for feed at substantially the same reaction conditions as in the previous runs.

The preparation of one of the catalysts will be outlined below:

Catalyst: (70Sb/30U 30(SiO 322.8 gms. of Sb O (White Star Grade M) and 136.2 gms. of U 0 Grade 1 were mixed with 800 cc. of c ncentrated nitric acid and heated for 45 minutes until fuming ceased. To this was added some water to cool the slurry, and 655.7 gms. of a 30% by weight colloidal suspension of silica in water and sufiicient ammonium hydroxide to obtain a pH of 8. The catalyst was filtered and washed with water, dried overnight at 120 C., calcined for 24 hours at 800 F. and heat-treated for 8 hours at 1725 F.

672 gms. were mixed with 373.3 gins. of a 30% by weight colloidal suspension of silica in water, in a high speed blender, and the mixture was extruded onto aluminum foil. This material was dried overnight at 120 C. and heat-treated for 6 hours at 1725 F.

EXAMPLES 13-15 Runs made with an antimony oxide-uranium oxide catalyst, set forth in Table II below, show conversions for the oxidation of allylbenzene to cinnamaldehyde at different temperatures, and for comparison, the conversion of it-methyl styrene to cinnamaldehyde at 460 C.

TABLE I Mole 1' ti Experb a 0 1 er pass conveislon to m Temp. Ci11namo- Benze- Atro o- Number Feed (.atalyst C. Feed Nils Air 1 nitrile nltr'ile niti ile liiih 1 Allylbenzene fi0(70Sb /30U)40(SiO2) 460 l 1.5 50 72.5 2 B Methylstyrene 60(70Sb/30U140(Si01) 450 1 1.5 50 72.5 a Allylheuzene 00(70Sb/30U)40(S1O5).... 410 1 1.5 50 72.5 4517 5'2 "i'i1' 2'4 4 B-Methybtyrcnc" (96Sb/5Fe)? 5101).. 450 1 1.5 50 72.5 5.1 14'4 1's 5 1 111 1115117.5115 75(95Shf5Fe)25(S1O2) 410 1 1.5 50 72.5 ms 813 is 1'3 6 a 5[)(BiqP1\1012052)501Si 410 1 1.5 50 72.5 5.1 4.6 0'9 0'7 7 44(Sl1 B lMo1205 55( p 4511 1 3.0 4&5 72.5 5.7 11.5 1513 g 4-L(Sb5.1]11 .1lM012U55-2)+5li(S1 410 1 3.11 48.5 72.5 12.5 4.6 1 5 1a ausmns svnrsno n-tmtsmu) 1 1.5 511 72.5 11.7 3.7 0'5 1 mantr -38511 05 4011 1 1.5 51] 72.5 11.5 15.5 110 ""55 1 2.5(Nt FoB1PMmzosm )+17.5(S102).. ass 1 1.5 50 72.5 11.11 5.0 1g as 8'2.5(N115.5FeSb5.5Bi5.5l\io11055)+1T.5(Si0:)- 7160 1 1.5 511 72.5 7.5 3.21.1.1111111111111'.

TABLE II Mole ratio Pet pass conversion to- Expvrilnr-nt. Pi-11111., WEE MM Number Fttll A lalnlyst. Fwd NIT: All N2 aldehyde dchydc deli ydu snouswsum10min. 41111 1 11 51.5 72.5 as as 60(70Sl1/30U1-1OKS10z) 410 1 11 51.5 72.5 24.5 1.2 n5... somuswanultorsion.. 4511 1 n 51.5 72.5 5.5 5.7 11:11

i claim: 1. A process for the manufacture of a compound having the structure wherein A is an aromatic group selected from the group consisting of phenyl, naphthyl, pyridyl, quinolyl, anthryl and phenanthryl radicals and R is selected from the group consisting of hydrogen and a lower alkyl group having from 1 to 4 carbon atoms, comprising reacting a monoolefinically substituted aromatic compound having the structure wherein A and R have the same connotation as above, with [reactants comprising ammonia and] molecular oxygen in the presence of the oxide of at least one metal element selected from the group consisting of antimony, uranium, iron, bismuth, nickel, manganese, thorium, cerium, tin, or in the presence of at least one salt of molybdic, phosphomolybdic, tungstic and phosphotungstic acids with at least one of the said metal elements, supported or unsupported by a catalyst support at about atmospheric pressure at a temperature in the range of 200 to 800 C.

2. The process of claim 1 in which the monoolefinically substituted aromatic compound is allylbenzene.

3. The process of claim 1 in which the monoolefinically substituted aromatic compound is allyl pyridine.

4. The process of claim 1 in which the operating pressure is at about atmospheric pressure.

5. The process of claim 1 in which the molar ratio of allylbenzene to air is in the range from 1:5 to 1:200.

6. The process of claim 1 in which the operating temperatures are in the range of from 350 to 500 C.

T. The process of claim 6 in which the catalyst is a fixed bed pelletized catalyst.

8. The process of claim 6 in which the catalyst is a fluidized bed spherulized catalyst.

9. The process of claim 8 in which the apparent contact time is in the range of 0.1 to 15 seconds.

References Cited The following references, cited by the Examiner, are of record in the patented file of this patent or the original patent.

UNITED STATES PATENTS 3,067,205 12/1962 Callighan et al. 260297 HENRY R. IILES, Primary Examiner S. D. WINTERS, Assistant Examiner U.S. Cl. X.R.

PO-ww UNITED STATES PATENT OFFICE (5/59) CERTIFICATE OF CORRECTION Patent No. RE 27,171 Dated September 97 Inventor(s) Robert K. Grasselli It is certified that error appears in the above-identified Patent and that said Letters Patent are hereby corrected as shown below:

Column l line 41, after "00" insert --l0--.

Columnj, line 56, "while" should be --which--.

Column 4, line 27, "table" should be "Table I--.

Signed and sealed this 29th day of February 1972.

(SEAL) Attest:

EDWARD M.FLETGHER,JR. ROBERT GOTTSGHALK Attesting Officer Commissioner of Patents 

